aqueous-phase organometallic catalysis 2ed 2004 - comils & hermann

Organometallic CatalysisEdited byBoy Cornils and Wolfgang A.Herrmann Aqueous-Phase Organometallic Catalysis, Second Edition Edited by Boy Cornils and Wolfgang A.. forma-The same is true

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Organometallic Catalysis

Edited byBoy Cornils and Wolfgang A.Herrmann

Aqueous-Phase Organometallic Catalysis, Second Edition

Edited by Boy Cornils and Wolfgang A Herrmann

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B Cornils, W A Herrmann (Eds.)

Applied Homogeneous Catalysis with Organometallic Compounds

Second, Completely Revised and Enlarged Edition

A de Meijere, F Diederich (Eds.)

Metal-Catalyzed Cross-Coupling Reactions

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Organometallic Catalysis Concepts and Applications

Edited by

Boy Cornils and Wolfgang A.Herrmann

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Prof Dr Boy Cornils

or other items may inadvertently be inaccurate Library of Congress Card No: applied for

A catalogue record for this book is available from the British Library.

Bibliographic information published

by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication

in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at

transla-Typesetting, printing and binding Konrad Triltsch

Print und digitale Medien GmbH Ochsenfurt-Hohestadt ISBN 3-527-30712-5

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Preface to the Second Edition

Very recently, some colleagues noticed a statement in one of the monthly columnsabout the state-of-the-art that “in organic chemistry reactions employing the sol-vent water are still rare [1]” – which is true and untrue at the same time: certainly,water-based conversions are scarce compared to those in the great majority of oth-

er solvents But whoever was sensitive enough to recognize the tremendous bilities of aqueous-phase catalysis would never ignore the increasing number ofpublications concerning this field of activity, the progress which has taken placeduring recent years, and the breakthroughs which have been brought about follow-ing these activities

possi-So it is a great pleasure for us to announce the second edition of our book ous-Phase Organometallic Catalysis – in such close proximity to the first edition in

Aque-1998 Responsible for this are on the one hand the dramatic successes of

industri-al reindustri-alization: production figures are now close to 1 MM tons per year in variousapplications (with hydroformylations, at approximately 800 000 tpy, in a senior po-sition) On the other hand, the long overdue in-depth occupation with the scientif-

ic basis, the exploratory work with the various possibilities of this “immobilizationwith the liquid support water”, and the exploitation of the immense variability ofthe method in chemical respects (regarding central atoms and ligands) create anatmosphere of overwhelming interest in this technique

Thus the sections of this revised edition have been enlarged to different extents.For instance, in respect of the scientific fundamentals and taking into account thatthe role of water in organometallic conversions is not only purely as a solvent but

as a strongly coordinative polar reagent It contributes considerably to the tion of polar or ionic intermediates or to oxidative additions to lower-valent transi-tion metal complexes (thus explaining the strong pH dependence of many aque-ous-phase catalyzed reactions) The work on different central atoms of catalyticallyactive complexes and the search for alternative, highly specialized ligands – includ-ing chiral ones – has extended considerably the scope of aqueous-phase organome-tallic catalysis together with knowledge about coordination catalysis

forma-The same is true for the application of water-soluble catalysts for quite a bunch

of basic organometal-derived chemical reactions ranging from hydrogenations or

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hydroformylations to more “exotic” applications such as water-based tive Diels – Alder reactions or kinetic resolutions It also includes improvementsand alternative answers for the chemical reaction engineering of aqueous-phasecatalyzed conversions.

enantioselec-Last but not least, the success of aqueous-phase catalysis has drawn the interest

of the homogeneous-catalysis community to other biphasic possibilities such as ganic/organic separations, fluorous phases, nonaqueous ionic liquids, supercriticalsolvents, amphiphilic compounds, or water-soluble, polymer-bound catalysts As inthe field of aqueous-phase catalysis, the first textbooks on these developmentshave been published, not to mention Joo´’s book on Aqueous Organometallic Cataly-sis which followed three years after our own publication and which put the spot-light on Joo´’s special merits as one of the pioneers in aqueous biphasic catalysis

or-Up to now, most of the alternatives mentioned are only in a state of intensivedevelopment (except for one industrial realization: that of Swan/Chematur forhydrogenations in scCO2[2]) but other pilot plant adaptations and even technicaloperations may be expected in the near future

This second edition is based mainly on the state-of-the-art as described in thepublished literature up to the year 2003 To make things easier and to avoid errors,parts of the second edition are revised and updated, rather than rewritten Thus,

in some cases the order of the references is unchanged and new references areadded without renumbering the existing ones (or substitute existing refs by newitems) The numbering of structures, equations, etc., was changed if necessary.Once more we have to express our thanks not only to the authors and coauthors

of the volume but also to the team at Wiley-VCH at Weinheim, especially Mrs.Claudia Grssl, for the production and their endless patience, and Dr Elke Maase,the publishing editor As with all our books, Mrs Diana Boatman from Redhill,Surrey (UK ), served as freelance copy-editor and was an invaluable help duringthe difficult process of completion The Munich research group, especially PD Dr

F E Khn, is acknowledged for scientific and technical assistance

References

[1] Nachr Chem 2003, 51(5), 516.

[2] B Cornils, W A Herrmann, R Schlgl, C.-H Wong, Catalysis from A to Z, 2nd Edition, Wiley-VCH, Weinheim, 2003, p 746.

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Preface to the First Edition

This book describes homogeneously catalyzed reactions under two major boundaryconditions: the catalysts employed are organometallic complexes that are used inthe aqueous phase In this respect the book is restricted to one area of homogene-ous catalysis and therefore – though substantially expanded and more detailed – toone special area of our previous book, Applied Homogeneous Catalysis with Organo-metallic Complexes ( VCH, Weinheim, Germany, 1996)

The subject of the book is the use of water-soluble organometallic catalysts forchemical reactions These catalysts are so far the sole successful means of imple-menting the idea of heterogenization of homogeneous catalysts by immobilizingthem with the aid of liquid supports They thus solve the cardinal problem of ho-mogeneous catalysis, which lies in the expensive separation of catalyst as well asproduct that is inherent in the system: the catalyst used in the homogeneousphase is separated by simply decanting the aqueous catalyst phase from the organ-

ic phase of the substrates and reaction products Since all attempts to heterogenizehomogeneous catalysts by immobilizing them on solid supports (“anchoring”)have to varying degrees been unsuccessful, only the use of homogeneous catalysts

in aqueous solution and thus on liquid supports (“biphase operation”) leads to aneat, inexpensive solution to the problem that conserves resources and is thereforeenvironmentally friendly

This book is restricted essentially to aqueous-phase catalyses and thus to one area

of the more comprehensively defined two-phase catalyses This restriction to themost recent and successful development of homogeneous catalysis takes account

of the rapid technical advances in the process concept first described by Manassen

et al in 1973, which was followed in rapid succession in the 1970s by hesitant sic work and in 1984 by the first commercial implementation This unusual se-quence – industrial implementation in a 100 000 tonnes per year oxo plant for thehydroformylation of propylene before years of time-consuming basic research todetermine mechanistic, kinetic and other data – demonstrates clearly the greatleap forward that this process development represented in the field of homogene-ous catalysis and in solving the central problem mentioned earlier Since then

ba-Aqueous-Phase Organometallic Catalysis, Second Edition

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other processes employing homogeneous catalysis have been converted to anaqueous two-phase procedure.

The development work intensified worldwide in various research groups in theyears following the first commercial implementation at Ruhrchemie AG in Ober-hausen The obvious course of action was to let colleagues and specialists them-selves report on their developments This led to the formation of the internationalcircle of contributors from the USA, France, the United Kingdom, China, Italy,Japan, India, Hungary and Germany which gives first-hand reports on its work.One focus of the book is the hydroformylation process, the process involved inthe first commercial implementation of aqueous-phase catalysis with its detaileddescriptions of fundamental laws, special process features, and the present state ofthe art Further focal points of the book are basic research on the complex catalysts(central atoms, ligands) and on the influence of the reaction conditions, solvents,and co-solvents, and a survey of other aqueous two-phase concepts and of pro-posed applications, with experimental examples and details Environmental as-pects are also considered

We are sure that the outline chosen and the wide range of contributions fromthe authors give a multifaced and informative picture of the present state of devel-opments in the field of aqueous two-phase catalysis, which presents not only theprinciples and accounts of the latest applications but also many aspects of spin-offs and alternative processes

This description of ideas and process developments appears to us to be highlyimportant for an appreciation of the potential of aqueous biphase catalysis The fa-miliar assessment of the most important aspects of heterogeneous and homogene-ous catalysis demonstrates that only in a solution of the problem of continuousseparation of catalyst and product, such as becomes possible with the processes in-volving aqueous immobilized catalysts, in the key to further progress found Onlyhomogeneous catalysts that can be handled without problems will give us scientistsand developers confidence that the clear and sure mechanistic understanding oftheir mode of action and the possibility of easy variability of steric and/or electron-

ic properties can be transferred to other immobilized, and thus easy-to-handle, alysts More optimistically, it is hoped that this will apply especially to those het-erogenized catalysts that basically are derived from tailor-made homogeneous cata-lysts

cat-The sharp line of demarcation between homogeneous and heterogeneous sis would thus be blurred and the possibility opened up of combining in one spe-cies the advantages of homogeneous catalysts and none of the disadvantages ofheterogeneous catalysts: heterogenized homogeneous catalysts would lead toequally advantageous results as homogenized heterogeneous catalysts – the long-awaited dream of catalysis research would be fulfilled!

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cataly-We thank the team at WILEY-VCH, especially Mrs Diana Boatman, Dr AnetteEckerle, and Mrs Claudia Grssl for their cooperation during preparation of thisbook and for helpful technical assistance.

Dipl.-Chem Kolja Wieczorek is acknowledged for preparing all formulas, ures, and schemes; Dipl.-Chem Thomas Weskamp for the total index

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1 Introduction

1 Introduction (B Cornils, W.A Herrmann) 3

2 Basic Aqueous Chemistry

2.1 Organic Chemistry in Water

(A Lubineau, J Auge´, M.-C Scherrmann) 27

2.1.1 Introduction 27

2.1.2 Origin of the Reactivity in Water 28

2.1.3 Pericyclic Reactions 30

2.1.3.1 Diels – Alder Reactions 30

2.1.3.2 Hetero Diels – Alder Reactions 32

2.2 Organometallic Chemistry in Water

( W.A Herrmann, F.E Khn) 44

2.2.2 Water as a Solvent and Ligand 44

2.2.3 Organometallic Reactions of Water 46

2.2.4 Catalytic Reactions with Water 50

2.2.4.1 Water-gas Shift Reaction 50

2.2.4.2 Wacker – Hoechst Acetaldehyde Process 50

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3 Catalysts for an Aqueous Catalysis

3.1 Variation of Central Atoms 71

3.1.1 Transition Metals (D.J Darensbourg, C.G Ortiz) 71

3.1.1.1 Introduction 71

3.1.1.2 Water-soluble Catalysts by Virtue of Water-soluble Ligands 72

3.1.1.3 Water-soluble Catalysts through Water Coordination 82

3.1.2 Lanthanides in Aqueous-phase Catalysis (S Kobayashi) 88

3.2.1 Monophosphines (O Stelzer†, S Rossenbach, D Hoff) 100

3.2.1.1 General Features, Scope, and Limitations 100

3.2.1.2 Anionic Phosphines 101

3.2.1.3 Cationic Phosphines 112

3.2.1.4 Nonionic Water-soluble Phosphines 115

3.2.2 Diphosphines and Other Phosphines (M Schreuder Goedheijt,

P.C.J Kamer, J.N.H Reek, P.W.N.M van Leeuwen) 121

3.2.2.1 General 121

3.2.2.2 Diphosphines – Introduction of Sulfonate Groups

by Direct Sulfonation 121

3.2.2.3 Introduction of Sulfonate Groups During Synthesis 123

3.2.2.4 Diphosphines with Quaternized Aminoalkyl or Aminoaryl Groups 125

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3.2.2.5 Diphosphines with Hydroxyalkyl or Polyether Substituents 125

3.2.3.3 Immobilization on Silica Supports 143

3.2.3.4 Macromolecular Ligands or Supports 145

3.2.3.5 Ligands not Containing Phosphorus 151

3.2.3.6 Additional Perspectives 154

3.2.4 Tenside Ligands (G Papadogianakis) 158

3.2.4.2 Tenside Phosphines and Amines 159

3.2.4.3 Hydroformylation Reactions Catalyzed by Transition Metal Surfactant –

3.2.4.6 Concluding Remarks and Future Prospects 171

3.2.5 Chiral Ligands ( W.A Herrmann, R.W Eckl, F.E Khn) 174

3.2.5.2 Sulfonated Chiral Phosphines 174

3.2.5.3 Other Water-soluble Chiral Ligands 181

3.2.5.4 Conclusions 185

3.2.6 Other Concepts (A Brner) 187

3.2.6.1 Hydroxyphosphines as Ligands 187

3.2.6.2 Amines and Polyoxometallates as Ligands

( W.A Herrmann, C.-P Reisinger) 194

4 Catalysis in Water as a Special Unit Operation

4.1 Fundamentals of Biphasic Reactions in Water

(Y nal, M Baerns, P Claus) 201

4.1.2 Gas/Liquid-phase Reactions 203

4.1.3 Gas/Liquid/Liquid-phase Reactions 207

4.1.4 Place of Reaction in Aqueous Biphasic Systems 212

4.2 Technical Concepts (A Behr) 219

4.2.1 Reaction Systems 219

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4.2.2 Technical Realization: Variations 221

4.2.2.1 Reaction with Product Separation 223

4.2.2.2 Reaction and Product Extraction 224

4.2.2.3 Reaction and Product Treatment 227

4.2.2.4 Reaction and Catalyst Separation 227

4.2.2.5 Reaction and Catalyst Extraction 229

4.2.2.6 Reaction and Catalyst Treatment 231

4.2.3 Reaction Engineering Aspects 233

4.5.2 Hydrolytic Reactions in Micelles 259

4.5.3 Oxidation Reactions in Micelles 260

4.5.4 Complex-catalyzed Hydrogenation in Micellar Media 2614.5.5 Carbon – Carbon Coupling Systems 264

4.5.6 Some Examples of Reactions in Reverse Micelles

under Phase-transfer Catalysis Conditions 275

4.6.1.3 Hydrogenations Mediated by Phase-transfer Catalysts 2784.6.1.4 Biphasic Transfer Hydrogenations 280

4.6.1.5 Aqueous/Organic-phase Oxidations Mediated by Metal

and PT Catalysts 280

4.6.1.6 Aqueous/Organic-phase Carbonylations 282

4.6.2 Counter-phase Transfer Catalysis (T Okano) 288

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4.6.2.2 Mechanism of the Counter-phase Transfer Catalytic Reaction 290

4.6.2.3 Counter-phase Transfer Catalytic Reactions 293

4.6.2.4 Concluding Remarks 297

4.6.3 Thermoregulated Phase-transfer and Thermoregulated Phase-separable

Catalysis (Z Jin, Y Wang, X Zheng) 301

4.6.3.2 Thermoregulated Phase-transfer Catalysis with Nonionic Water-soluble

Phosphines 302

4.6.3.3 Hydroformylation of Higher Alkenes Based on TRPTC 305

4.6.3.4 Thermoregulated Phase-separable Catalysis 307

4.7 Transitions to Heterogeneous Techniques (SAPC and Variations)

(M.E Davis) 313

4.7.2 The SAPC Concept of Immobilization 314

4.7.3 Example of Rational Catalyst Design Strategy 318

4.7.4 Suggested Reactions for Implementation of Design Concepts 321

4.7.5 Outlook 322

5 Aqueous Catalysts for Environment and Safety

5.1 Water-soluble Organometallics in the Environment

( W.A Herrmann, F.E Khn) 327

5.1.2 Biological Methylation 327

5.1.3 Cobalamines – Organometallics in Nature 328

5.1.4 Organoarsenic and Organotin Compounds 330

5.2.2 The Ruhrchemie/Rhoˆne-Poulenc (RCH/RP ) Process 338

5.2.3 Crucial Environmental Improvements 342

5.2.4 Conclusions 345

6 Typical Reactions

6.1 Hydroformylation 351

6.1.1 Development of the Commercial Biphasic Oxo Synthesis

(B Cornils, E.G Kuntz) 351

6.1.1.1 History of Biphasic Catalysis 351

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6.1.1.2 Basic Work and Investigations by Rhoˆne-Poulenc 353

6.1.1.3 Investigations by Ruhrchemie AG 355

6.1.1.4 The RCH/RP Process as the Final Point of Development 358

6.1.2 Kinetics (R.V Chaudhari, B.M Bhanage) 364

6.1.2.2 Kinetics Using Water-soluble Catalysts 365

6.1.2.3 Concluding Remarks 375

6.1.3 Reaction of Alkenes 377

6.1.3.1 Lower Alkenes (C.D Frohning, C.W Kohlpaintner) 377

6.1.3.2 Higher Alkenes (H Bahrmann, S Bogdanovic,

P.W.N.M van Leeuwen) 391

6.1.3.3 Functionalized Alkenes (E Monflier, A Mortreux) 410

6.1.4 Re-immobilization Techniques (H Bahrmann) 417

6.1.4.2 Water-insoluble, Re-immobilized Liphophilic Ligands and

Their Separation by Membrane Technique 418

6.1.4.3 Separation and Use of Water-insoluble Ammonium Ligands

6.2.3.1 Hydrogenation of Compounds with C¼C and CC Bonds 441

6.2.3.2 Hydrogenation of Compounds with C¼O and C¼N Bonds 451

6.2.3.3 Hydrogenolysis of CO, CN, CS, and C – Halogen Bonds 4566.2.3.4 Miscellaneous Hydrogenations 458

6.3 Hydrogenation and Hydrogenolysis of Thiophenic Molecules

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6.4.2 Wacker-type Oxidations (E Monflier, A Mortreux) 481

6.4.2.1 Possibilities of Wacker-type Oxidations 481

6.4.3 Methyltrioxorhenium( VII ) as an Oxidation Catalyst

(F.E Khn, W.A Herrmann) 488

6.4.3.2 Synthesis of Methyltrioxorhenium( VII ) 488

6.4.3.3 Behavior of Methyltrioxorhenium in Water 489

6.4.3.4 Catalyst Formation and Applications in Alkene Epoxidation 490

6.4.3.5 Other Oxidation Reactions 494

6.6 CC Coupling Reactions (Heck, Stille, Suzuki, etc.)

( W.A Herrmann, C.-P Reisinger, P Hrter) 511

6.7.2.1 Michael Additions of HCN to Activated Alkenes 524

6.7.2.2 Synthesis of Cyanohydrins from Ketones and Aldehydes 525

6.7.2.3 Strecker Synthesis of Aminonitriles 526

6.7.2.4 HCN Addition to Unactivated C¼C Double Bonds 526

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6.7.2.5 Cyanide Coupling Reactions 528

6.10.2 “Classical” Group VIII Catalysts 551

6.10.3 Polymers Prepared via Aqueous ROMP 554

6.10.4 Alkylidenes as Catalysts 556

6.10.4.1 Well-defined Ruthenium Alkylidenes 556

6.10.4.2 Water-soluble Alkylidenes 557

6.10.5 Summary 564

6.11 Asymmetric Synthesis (D Sinou) 567

6.12 Catalytic Polymerization (S Mecking) 576

6.12.2 Copolymerization of Carbon Monoxide with Alkenes 577

6.12.3 Polymerization of Ethylene and 1-Alkenes 578

6.12.4 Polymerization of Conjugated Dienes 581

6.12.5 Vinyl-type Polymerization of Cyclic Alkenes 582

6.12.6 Ring Opening Metathesis Polymerization 583

6.12.7 Polymerization of Alkynes 587

6.12.8 Polymerization by Suzuki Coupling 587

6.12.9 Summary and Outlook 589

6.13 Oleochemistry (A Behr) 593

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6.13.8 Isomerization 603

6.14 Halogen Chemistry (M Bressan, A Morvillo) 606

6.14.2 Reductive and Oxidative Dehalogenation 606

6.14.3 Coupling and Carbonylation Reactions 609

6.15 Biological Conversions (P.J Quinn) 613

6.15.2 Biological Substrates 613

6.15.3 Hydrogenation of Unsaturated Lipids in Aqueous Dispersions 614

6.15.3.1 Water-insoluble Homogeneous Catalysts 616

6.15.3.2 Water-soluble Homogeneous Catalysts 617

6.15.3.3 Sources of Hydrogen 619

6.15.4 Hydrogenation of Biological Membranes 620

6.15.4.1 Topology of Unsaturated Lipids in Membranes 620

6.15.4.2 Function of Unsaturated Lipids in Membranes 621

6.15.4.3 Acclimation of Membranes to Low Temperature 622

6.15.4.4 Membrane Unsaturation and Stability at High Temperatures 622

6.15.4.5 Biochemical Homeostasis of Unsaturated Lipids 623

6.15.4.6 Hydrogenation of Living Cells 624

6.16.8 Synthesis of Various Heterocycles 633

7 Other Biphasic Concepts

7.1 Nonaqueous Organic/Organic Separation (SHOP Process)

7.2.2 The Fluorous Concept 646

7.2.3 Process and Applications 650

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7.3 Nonaqueous Ionic Liquids (ILs, NAILs) (H Olivier-Bourbigou) 6557.3.1 Introduction 655

7.3.2 NAILs as a New Class of Solvents 655

7.3.3 Applications in Organic Synthesis and Catalysis 657

7.3.3.1 Salts Containing Strongly Coordinating Anions to Stabilize Anionic

Complexes 657

7.3.3.2 Salts Containing Weakly Coordinating Anions for Cationic

and Molecular Complexes 658

7.3.3.3 Salts Containing Chloroaluminate Anions as Solvents and Acidic

Catalysts 660

7.3.3.4 Supported Ionic Liquid Catalysis 661

7.3.3.5 Solvents for Organic Reactions 661

7.3.4 Concluding Remarks 662

7.4 Immobilization of Organometallic Catalysts Using Supercritical

Fluids ( W Leitner, A.M Scurto) 665

7.4.2 Practical Approaches to Multiphase Catalysis Involving Supercritical

Fluids 668

7.4.2.1 Supercritical Fluids and Supported Catalysts 668

7.4.2.2 Liquid/Supercritical Biphasic Systems 672

7.4.2.3 Catalysis and Extraction Using sc Solutions (CESS ) 678

7.4.3 Conclusions and Outlook 682

7.5 The Amphiphilic Approach (P.C.J Kamer, J.N.H Reek,

P.W.N.M van Leeuwen) 686

7.5.1 Separation Methods 686

7.5.1.1 Two-phase Catalysis 686

7.5.1.2 The Extraction Concept 688

7.5.2 Use of Amphiphilic Phosphines 690

7.5.2.1 Catalysis Using Amphiphilic Ligands 690

7.5.2.2 Distribution Characteristics of the Free Ligands 693

7.5.2.3 Rhodium Recycling 696

7.6 Catalysis with Water-soluble Polymer-bound Ligands

in Aqueous Solution (S Mecking, E Schwab) 699

7.6.2 Catalysis with Water-soluble Polymer-bound Ligands

in Aqueous Solution 700

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8 Aqueous-phase Catalysis: The Way Ahead

8.1 State of the Art (B Cornils, W.A Herrmann) 709

8.2 Improvements to Come 712

8.2.1 Reaction Engineering 713

8.2.2 Other Technologies 714

8.2.3 Other Feedstocks and Reactions 715

8.3 Focal Future Developments 717

Subject Index 727

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Prof Dr Manfred Baerns

Institut fr Angewandte Chemie

D-44227 Dortmund/GermanyTel: þ 49/231 755 2310Fax: þ 49/231 755 2311E-mail: arno.behr@bci.uni-dortmund.deProf Dr Matthias Beller

Leibnitz-Institut fr Organische Katalyse

an der Universitt RostockBuchbinderstr 5 – 6D-18055 Rostock/GermanyTel: þ 49/381 466 9313Fax: þ 49/381 466 9324E-mail: Matthias.Beller@ifok.uni-rostock.de

Dr Bhalchandra M BhanageDivision of Materials Science andEngineering

Hokkaido UniversityKita 13 Nishi 8, Kita-kuSapporo 060-8628/JapanTel: þ 81/11706 6597Fax: þ 81/11706 6594E-Mail: bhanage@proc-ms.eng.hokudai.ac.jp

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Dr Claudio Bianchini

Istituto per lo Studio della Stereochimica

ed Energetica dei Composti

Wilmington, Delaware 19880-0302/USATel: þ 1/302 695 3761

Fax: þ 1/302 695 9084E-mail: Bryndza@esvax.enet.duPont.comProf Dr Raghunath V ChaudhariNational Chemical LaboratoryPune 411 008/India

Tel: þ 91/2025 893 163Fax: þ 91/2025 893 260E-mail: rvc@ems.ncl.res.inProf Dr Peter ClausTechnische Universitt DarmstadtInstitut fr Technische Chemie undMakromolekulare Chemie

Petersenstr 20D-64287 Darmstadt/GermanyTel: þ 49/6151 16 5369Fax: þ 49/6151 16 4788E-mail: claus@ct.chemie.tu-darmstadt.de

Prof Dr Boy CornilsKirschgartenstr 6D-65719 Hofheim/GermanyTel: þ 49/6192 23502Fax: þ 49/6192 23502E-mail: boy.cornils@t-online.deProf Donald DarensbourgTexas A&M UniversityDepartment of Chemistry

PO Box 30012College Station, Texas 77892-3012/USATel: þ 1/979 845 5417

Fax: þ 1/979 845 0158E-mail: djdarens@mail.chem.tamu.edu

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Prof Dr Mark E Davis

Chemical Engineering

California Institute of Technology

Pasadena, California 91125/USA

and Chemical Engineering

California Institute of Technology

Pasadena, California 91125/USA

Department of ChemistryCollege of Arts and SciencesBlacksburg, Virginia 24061-0212/USATel: þ 1/540 231 7206

Fax: þ 1/540 231 3255E-mail: hanson@vt.edu

Dr John A Harrelson, Jr

DuPont NylonExperimental Station, Bldg 302P.O Box 80328

Wilmington, Delaware 19880-0302/USATel: þ 1/302 695 3761

Fax: þ 1/302 695 9084

PD Dr Peter HrterTechnische Universitt MnchenAnorganisch-chemisches InstitutLichtenbergstr 4

D-85747 Garching/GermanyTel: þ 49/89 2891 3099Fax: þ 49/89 2891 3473E-mail: peter.haerter@ch.tum.deProf Dr Wolfgang A HerrmannPresident of the

Technische Universitt MnchenArcisstr 21

D-80333 Mnchen/GermanyTel: þ 49/89 2892 2200Fax: þ 49/89 2892 3399E-mail: sekretariat.ac@ch.tum.de

Dr Dietmar HoffRheinchemiePaul-Ehrlich-Str 10D-67122 Altrip/GermanyE-mail: dietmar.hoff@rheinchemie.com

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Prof Dr Istva´n T Horva´th

Etvs University

Department of Chemical Technoloy

and Environmental Chemistry

Pa´zma´ny Pe´ter se´ta´ny 1/A

H-1117 Budapest/Hungary

Tel: þ 31/1 2090590

Fax: þ 31/1 2090607

E-mail: istvan.t.horvath@hit-team.net

Prof Dr Zilin Jin

State Key Laboratory of Fine Chemicals

Dalian University of Technology

116012 Dalian/China

Tel: þ 86/411 467 1511

Fax: þ 86/411 363 3080

E-mail: hpcuo@mail.dlptt.ln.cn

Prof Dr Ferenc Joo´

University of Debrecen and

Hungarian Academy of Sciences

Prof Dr Philippe Kalck

Ecole Nationale Supe´rieure

des Inge´nieurs en Arts Chimiques

Nieuwe Achtergracht 166NL-1018 WV AmsterdamThe NetherlandsTel: þ 31/20 525 6495/6454Fax: þ 31/20 525 6456

Dr Agnes Katho´

University of Debrecen andHungarian Academy of SciencesP.O Box 7

H-4010 Debrecen/HungaryTel: þ 36/52 512 900Fax: þ 36/52 512 915E-mail: katho@tigris.klte.huProf Dr Shu KobayashiGraduate School of PharmaceuticalSciences

The University of TokyoHongo, Bunkyo-kuTokyo 113-0033/JapanE-Mail: skobayas@mol.f-u-tokyo.ac.jp

Dr Christian W KohlpaintnerChemische Fabrik BudenheimRheinstr 27

D-55257 Budenheim/GermanyTel: þ 49/6139 89495

Fax: þ 49/6139 89464E-mail: ckohlpaintner@budenheim-cfb.com

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Dr Jrgen G.E Krauter

Prof Dr Ga´bor Laurenczy

Institut de Chimie Minerale et

Nieuwe Achtergracht 166NL-1018 WV AmsterdamThe NetherlandsTel: þ 31/20 525 5419Fax: þ 31/20 525 6422E-mail: pwnm@anorg.chem.uva.nlProf Dr Walter Leitner

Lehrstuhl fr Technische Chemieund Petrolchemie

RWTH-AachenWorringer Weg 1D-52056 Aachen/GermanyTel: þ 49/241 802 6480Fax: þ 49/241 802 2177E-mail: leitner@itmc.rwth-aachen.deProf Dr Andre´ Lubineau

Laboratoire de Chimie OrganiqueMultifonctionnelle

Universite´ de Paris-SudBat 420

F-91405 Orsay/FranceTel: þ 33/169 157 233Fax: þ 33/169 154 715E-mail: lubin@icmo.u-psud.fr

Dr David M LynnLaboratories of ChemistryCalifornia Institute of TechnologyPasadena, California 91125/USATel: þ 1/626 395 6003

Fax: þ 1/626 564 9297

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Istituto per lo Studio della Stereochimica

ed Energetica dei Composti

Faculte´ des Sciences J Perrin/

Laboratoire de Physicochimie des

Prof Dr Andre´ Mortreux

Universite´ des Sciences et Technologies

I-35100 Padova/ItalyTel: þ 39/49 827 5156Fax: þ 39/49 827 5161Prof Dr Gnther OehmeInstitut fr Organische Katalyseforschung

an der Universitt Rostock e V

Buchbinderstr 5 – 6D-18055 Rostock/GermanyTel: þ 49/381 466 930Fax: þ 49/381 466 9324E-mail: guenther.oehme@ifok.uni-rostock.de

Prof Dr Tamon OkanoDepartment of Materials ScienceFaculty of Engineering

Tottori UniversityTottori 680/JapanTel: þ 81/857 31 5260Fax: þ 81/857 31 0881E-Mail: okano@che.tottori-u.ac.jpProf Dr He´le`ne Olivier-BourbigouInstitut Franais du Pe´trole

1 – 4 Avenue de bois Pre´auF-92852 Rueil-Malmaison Ce´dexFrance

Tel: þ 33/1 475 26779Fax: þ 33/1 475 26055E-mail: helene.olivier-bourbigou@ifp.fr

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Dr Ycel nal

Technische Universitt Darmstadt

Institut fr Technische Chemie und

Prof Dr Peter J Quinn

King’s College London

Nieuwe Achtergracht 166NL-1018 WV AmsterdamThe NetherlandsTel: þ 31/20 525 6437Fax: þ 31/20 525 6422E-mail: reek@science.uva.nl

Dr Claus-Peter ReisingerBusiness DevelopmentExatec LLC

31220 Oak Creek DriveWixom, Michigan 48393/USAE-Mail: www.exatec.biz

Dr Stefan RossenbachBergische UniversittGauss-Str 20D-42047 Wuppertal

Dr Ana M SantosTechnische Universitt MnchenAnorganisch-chemisches InstitutLichtenbergstr 4

D-85747 Garching/GermanyTel: þ 49/89 2891 3102Fax: þ 49/89 2891 3473E-mail: ana.kuehn@ch.tum.de

Dr Marie-Christine ScherrmannLaboratoire de Chimie OrganiqueMultifonctionelle

Universite´ de Paris-Sud, Bat 420F-91405 Orsay/France

Tel: þ 33/1691 54719Fax: þ 33/1691 54715E-mail: mcscherr@icmo.u-psud.fr

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Dr Marcel Schreuder Goedheijt

Prof Dr Roger A Sheldon

Delft University of Technology

Department of Organic Chemistry

Laboratoire de Synthe`se Asyme´triqueU.M.R U.C.B.L./C.N.R.S 5622

43, Bd du 11 Novembre 1918F-69622 Villeurbanne Ce´dex/FranceTel: þ 33/472 446 263

Fax: þ 33/472 448 160E-mail: Denis.Sinou@univ-lyon.frProf Dr Othmar Stelzer †Formerly:

Bergische Universitt Wuppertal

Dr Martine UrrutigoityEcole Nationale Supe´rieure desInge´nieurs en Arts Chimiques etTechnologique (ENSIACET )

118, Route de NarbonneF-31077 Toulouse Cedex 04/FranceTel: þ 33/562 885 703

Prof Dr Dieter VogtEindhoven University of TechnologySchuit Institute of Catalysis STW 3.29

PO Box 513NL-5600 MB EindhovenThe NetherlandsTel: þ 31/40 247 2730Fax: þ 31/40 245 5054E-mail: d.vogt@tue.nlYanhua WangState Key Laboratory of Fine ChemicalsDalian University of Technology

116012 Dalian/China

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Tel: þ 86/411 467 1511Fax: þ 86/411 363 3080

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Introduction

Boy Cornils, Wolfgang A Herrmann

“For it is one thing to invent a basically correct process, another

to introduce it in industry”

“Denn [eines] ist es, ein prinzipiell richtiges Verfahren zu erfinden,ein anderes, es in die Industrie einzufhren.”

Hermann Ost [1]

Well disposed critics think that heterogeneous catalysis [2] is still at a stage of

blind-ly groping empiricism and therefore at the level of a “black art” [3] This statement,which has not remained uncontradicted [4], is in complete unison with the result

of a comparison of heterogeneous with homogeneous catalysis (cf Table 1 [5]).Echoing the above criticism, the comparison under “variability of steric and elec-tronic properties” and “mechanistic understanding” showed an advanced under-standing of elementary steps in homogeneous catalysis Yet Table 1 also lists themajor industrial disadvantage of homogeneous catalysis: the immense difficulty

of catalyst recycling, which is responsible for the fact that about 80% of catalyticreactions still employ heterogeneous catalysts and only 20% involve homogeneouscatalysts This is because it is inherently difficult to separate the molecularly dis-solved homogeneous catalyst from the reaction products and any unconverted re-actants in which the catalyst is likewise dissolved at a molecular level Particularly,homogeneous organometallic catalysts while being recycled/worked-up, e.g., byusing distillation or chemical techniques, suffer from thermal or chemical stress.Table 2 shows this and in detail in a comparison of homogeneous two versions ofheterogeneous catalyses [6 b]

Tables 1 and 2 immediately suggest as a practical solution that a tion” of homogeneous catalysts, i.e., the immobilization or anchoring of dissolvedcatalysts on immobile, solid supports, may be a way of transferring many of theadvantages of heterogeneous catalysis to homogeneous systems In theory, a het-erogenized (immobilized) homogeneous catalyst should behave like a hetero-geneous catalyst and solve the problem of catalyst recycling, provided the attend-

“heterogeniza-Aqueous-Phase Organometallic Catalysis, Second Edition

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ant diffusion problems – the significant disadvantage of heterogeneous catalysis –prove tolerable.

Since solving this recycling problem is essential for the high-volume processes ofhomogeneous catalysis (for hydroformylation especially: annual output was about6.5 million tonnes in 1996 [7]; this figure has now augmented to 9.2 MM tpy [7 b]),legions of scientists have published innumerable papers demonstrating ways ofachieving heterogenization by the anchoring of homogeneous catalysts Many ofthe sometimes very ingenious methods tried to date (including poly- or copolymeri-zation of catalytically active and polymerizable monomers, functionalization of suit-able supports and introduction of catalytically active constituents, precipitation ofmetals, or impregnation of suitable supports with active catalyst precursors, etc.[8, 9]) did indeed lead to initially active, “heterogenized” catalysts However, it wasalso found that, despite coordination-capable support groups and covalent bonds,all these catalysts have only a finite on-stream life due to the leaching which startsfrom the first minute of use This leaching always affects not only the (usually cost-ly) central atoms but also the (frequently more costly) ligands of homogeneousmetal complex catalysts The economic need to recover them more than offsets thesaving due to simplified recycling Whistling in the dark is not problem-solving: atpresent, despite sporadic news of success, there is no economical process for heter-ogenizing homogeneous catalysts of large industrial processes

Variability of steric and electronic

properties of catalysts

random conditions

More or less impossible

describes the way in which a catalyst is formed, employed, separated or deposited, made-up, and regenerated or recovered, “catalyst cycle” is the visual interpretation of a complex reaction mechanism by subdividing the overall reaction into a series of ad- and desorption steps (with heterogeneous catalysts) or arranging the intermediates of a homogeneously catalyzed reaction in a logical sequence to form a closed cycle This gives rise to the well-known catalytic cycles of homogeneous catalysis (cf a multitude of examples in the course of the following chapters) [38 a– c].

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There is little mileage in looking for ostensibly more and more effective ligandsand better and better optimization of support and catalyst precursor to ensure, onthe one hand, adequate immobilization on the support (sufficient stability of thecovalent bond between support matrix and central atom) and, on the other, ade-quate mobility for the catalytically active catalyst constituents (sufficient lability ofthe ligand sphere of the metal atom) All the results so far allow only the conclu-sion that the heterogenizing techniques used had to remain unsuccessful The rea-son for this is that the various catalyst species undergo changes in spatial configu-ration as they pass through the catalytic cycle typical of a homogeneous process.The constant “mechanical” stress on the central atom $ ligand bonds and theconstant change in the bond angles and lengths ultimately lead also to a weaken-ing of the central atom $ support bond This is conveniently demonstrated usingthe hydroformylation catalyzed by heterogenized cobalt carbonyls as an example(Fig 1) The catalyst passes through the two forms of a trigonal-bipyramidal and

of a tetrahedral cobalt carbonyl, which overstresses and weakens the ing bond Co $ support

heterogeniz-A more elegant and ultimately more successful solution is the idea, probablyfirst articulated and systematized by Manassen [10], although Papadogianakis andSheldon [11] mistakenly credit Bailar [9], of an immobilization with the aid of a

“liquid support” In 1972 Manassen suggested

“ the use of two immiscible liquid phases, one containing the catalyst and the other taining the substrate ”

con-and hence the general form of biphase catalysis, which constitutes a logical opment of the work in “molten salt media” (known today as “ionic liquids”; thisterm used to refer to high-melting, inorganic salts or salt mixtures [12]) described

devel-by Parshall [13] Interestingly, the inventors of Shell’s SHOP process, who hadalready worked on soluble, homogeneous complex catalysts in a biphase system

Homogeneous catalysis

Heterogeneous catalysis

chemical decomposition;

problems Distillation

Extraction

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some years earlier [14], cited the special method without particular emphasis,judging by the wording in the first patents Shell seems not to have been awareimmediately that it had laid its hands on the key to the novel technology of homo-geneous catalysis by means of immobilized catalysts on liquid supports – albeitnot water (cf Section 7.1).

The basic principles of biphase catalysis is accordingly that the homogeneouscatalyst is in solution in one of the phases and the reaction products are located in

a second phase which is immiscible with the catalyst phase – “heterogeneous” –and are therefore easy to separate off (see below)

The specific form of aqueous biphase catalysis was very significantly stimulated

by the work of Joo´ and Beck at Debrecen (in relation to hydrogenation especially[15]; cf Section 6.2) and Kuntz at Rhoˆne – Poulenc (hydroformylation, telomeriza-tion [16] cf Section 6.1.1), following Manassen’s work, which was then unfortu-nately merely theoretical Three years after the first edition of this book Joo´’s workabout “Aqueous Organometallic Catalysis” appeared in 2001 [39] Quite unusual,

in “A personal look at the history of aqueous organometallic catalysis” he tookdown on record his important share of the development of this new field of activi-

ty We all know Joo´ as the earliest pioneer and can now acknowledge that his firstpublications appeared simultaneously (but somewhat hidden among Hungarianjournals) to that of Manassen et al [40] Therefore, the ideas were developed inde-pendently from each other and leave Joo´ as a man of merit within the historicalassessment The mentioned book of Joo´, by the way, is meritorious because it fo-cusses especially on the hydrogenation as a well suitable application of aqueous-phase catalysis Remarkably, the fundamental papers of Joo´ and Kuntz created lit-tle interest and only found a wider echo in academic research once Ruhrchemie

AG had managed to achieve industrial scale-up of aqueous biphase catalysis in anoxo process (cf Section 6.1 [17]) In a drastic departure from the normal pattern,here basic research lagged considerably behind industrial research and application

course of the catalytic hydroformylation cycle.

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Reviews, even recent ones, tend to concentrate more on the state of basic researchthan on that of the large-scale industrial processes [11, 18], and curiously there arereviews appearing even now which fail to cite the contributions made by industry(see [19]!) In addition, it has to be mentioned as typical of this very recent devel-opment of homogeneous catalysis that considerable areas of the art and of its ad-vances are chronicled in patents Anyone who knows of the reluctance of basic re-searchers to read patents knows what this means for the current awarenessamongst workers in basic research on biphasic catalysis.

In a technology involving two liquid phases, one of which contains the metalcomplex catalyst in solution, the idea of using water as one of the phases is notnecessarily obvious Hydroformylation, in 1972 – the time of Manassen’s idea –the most important application of homogeneous catalysis, utilized cobalt catalysts,whose handling sensitivity ruled out an aqueous phase Or, as P Cintas [20] wrote,

“At first, the idea of performing organometallic reactions in water might seem ridiculous, since it goes against the traditional belief that most organometallics are extremely sensitive

to traces of air and moisture and rapidly decompose in water.”

This is all the more surprising as the history of the oxo process actually prescribedthe use of aqueous catalysts and catalyst precursors (aqueous cobalt salts as pre-cursors of the earlier “Diaden” process [21], the at least partially aqueous cycle ofthe BASF and Kuhlmann process [22 b], or the cleavage of solvent-soluble by-prod-ucts and heavy ends of the oxo process with the aid of water-dissolved metal salts[22 c, 23])

The advantage of using water is that it is easy to separate from organic products,

as indicated by Manassen in a continuation of the above quotation [10]:

“The two phases can be separated by conventional means and high degrees of dispersion can

be obtained through emulsification This ease of separation may be particularly advantageous

in situations where frequent catalyst regeneration is required”.

Figure 2 illustrates the enormous importance of the biphase technique for geneous catalysis: the aqueous catalyst solution is charged in the reactor with thereactants A and B, which react to form the solvent-dissolved reaction products Cand D C and D are less polar than the aqueous catalyst solution and are thereforesimple to separate from the aqueous phase (which is recycled directly into the re-actor) in the downstream phase separator (decanter)

homo-The advantage of the “liquid support” water and of its high affinity for the metalcomplex catalyst is evident The catalyst is heterogenized with respect to the organ-

ic reaction products C and D and therefore can not only be separated from theproducts in the “other phase” (possibly including unconverted reactants A and B ),but also immediately thereafter starts a new cycle of the catalytic cycle process.Aqueous biphase catalysis is therefore – intentionally – located between hetero-geneous and homogeneous catalysis, as illustrated in Figure 3 Special attention

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Fig 2 Principle of biphase catalysis illustrated for the reaction A þ B ! C þ D.

variation of the application phase of catalysts FBS, fluorous biphase system (cf Section 7.2 [24]; PEG, polyethylene glycol cf Sections 4.6.3 and 6.1.3.2; SAPC, and SLPC, cf Section 4.7) NAIL, non-aqueous ionic liquids (cf Section 7.3).

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may be drawn to the somewhat confusing and ambiguous use of the terms mogeneous” and “heterogeneous” in the context of homogeneous/heterogeneouscatalysis and homogeneous/heterogeneous phase variation: the catalytic systemworks homogeneously despite heterogeneous phase variation.

for the reaction A þ B ! C þ D (4.1) Aqueous biphase operation;

(4.2) membrane technique; (4.3) thermal methods; (4.4) chemical

treatment [22 a].

Tiêu đề	Aqueous-Phase Organometallic Catalysis
Tác giả	Boy Cornils, Wolfgang A. Hermann
Trường học	Technische Universität München
Chuyên ngành	Organometallic Catalysis
Thể loại	Sách giáo trình
Năm xuất bản	2004
Thành phố	Weinheim

Định dạng
Số trang	781
Dung lượng	5,26 MB